Geochimica et Cosmochimica

Acta, 1963, Vol. 27, pp. 525to 546. Pergamon Press Ltd. Printedin Northern
Ireland

The flame photometric determination of potassium in geological

materials used for potassium argon dating
JOHN A. COOPER
Dept. of Geophysics, Australian National University, Canberra, Australia

(Received 17 October 1962)

Abstract-An investigation has been made of factors contributing to the spread of 5 per cent which
exists in interlaboratory comparisons of the potassium content of materials used for K-Ar age
determinations. It has been found for flame photometric determinations that the interference
of other ions present in the solutions obtained depends markedly on the burner used, on the fuel,
and also on the actual potassium concentration.
Flame photometric figures are compared with those obtained by isotope dilution in the same
laboratory and show satisfactory agreement.
As a further check a comparison is made of the agesdetermined on several minerals, including
pyroxenes, extracted from the same rock.
Potassium analyses are reported for several N.B.S., and other, interlaboratory standards.
Recommendations for procedures to eliminate interferences found in the more common
materials analysed for dating purposes are set out in an appendix.

INTRODUCTION
POTASSIUM-ARGON dating of rocks and minerals demands both high precision and
absolute accuracy for the potassium determinations. For example, errors of f5
per cent in analysis involving rocks of the Silurian Period (405-435 x lo6 years
(EVERNDEN and RICHARDS, 1962; KULP, 1961)) would give a spread of greater
than the length of the period. A total error of the order of f0.5 per cent is neces-
sary if age data are to be stratigraphically useful. It is usually possible to obtain
a precision of this order with modern flame photometric measurements, but a
comparison of interlaboratory determinations of the same sample (e.g., M.I.T.
biotite B-3203, PINSON, 1961) reveal differences greater than 5 per cent, although
the precision given by the individual laboratories is often much better.
The minerals and rocks used for age determinations contain some or all of the
following cations as major constituents: Si, Al, Fe, Ca, Mg, Na, K. Assuming acid
digestion of the sample, Si is volatilized as fluoride, and the remaining elements
are left as sulphates or perchlorates. Some workers use this solution directly in
the flame photometer, with or without added internal standard. However it is
very common to remove Fe and Al (the R,O, group) by ammonia precipitation
and by addition of ammonium carbonate. The resulting solution containing K,
Na, Mg and ammonium salts is then used for the flame photometric determination.
PINSON (1958) has reviewed some of the specific problems of potassium determin-
ations on micas for age work. Many reports of interelement and anion effects in
flame photometry have been made (DEAN, 1960; HAVRE, 1961). There is, how-
ever, much inconsistency in the conclusions of different writers. The number and
variety of interferences reported seems to point to the need for separation of as
525
526 JOHNA. COOPER

many extraneous elements as possible and to the use of standards as close in com-
position as possible to the samples being analysed. POLUEETOV (1961) quotes data
derived from work with an air acetylene flame. An adaption of his graph illus-
trating sodium enhancement of potassium emission is included as Fig. 3 to show
how the effect is vitally dependent on the concentration of both sodium and potas-
sium. The practical result of this is that different weights of a certain sample, or
different dilutions of equal weights of that sample can give different answers.
Much higher levels of Na concentration are said to cause depression of K emission.
He records that the colder illuminating gas flame gives only “very small enhance-
ment of K by Na except at very low K levels” e.g., “5 per cent enhancement at
4 p.p.m. K”. He recommends buffering of standards and unknowns with excess
sodium until a plateau is reached. BAKER and GARTON (1961) report similar alkali
enhancement of K emission from experiments with propane-oxygen and propane-
air fuel mixtures. ABBEY and MAXWELL (1960) using a Beckman instrument with
acetylene-oxygen fuel report interference by magnesium. They state that for a
40 p.p.m. K solution the presence of 50-500 p.p.m. of Mg caused a constant 3%
depression of K emission. For the analysis of biotites they recommended the
addition of 100 p.p.m, Mg to standard and unknown solutions after the separation
of Fe and Al.
In summary, the addition of large amounts of an interfering element is com-
monly used to provide a type of buffering action. This has the effect of creating
a matrix common to the standards and samples, bringing them both close to the
same physical, chemical and ionic condition within the flame.

Observed systematic differences in potassium determinations

The original chemical treatment of samples used in this laboratory ( EVERNDEN
and RICHARDS, 1962) involving acid digestion and cation separation is set out in
Appendix I. Equivalent amounts of the various chemicals remaining in the sample
solutions were added to the standard K solutions. Most of the samples were bio-
tites and plagioclases with a few K-feldspars and muscovites. These first three
mineral types would have Mg, Na, and Na, respectively, left in solution after cation
separation. Work was begun using a Beckman D.U. spectrophotometer with a
model 9200 flame photometer attachment, using Hz-O, as fuel. Subsequent meas-
urements on the same solutions with a Perkin Elmer 146 flame photometer operated
as a single channel instrument yielded results systematically higher by as much
as 7 per cent (see Table I*). This observation validates the conclusion reached by
PINSON (1958).
Plagioclase solutions also gave higher results with the Perkin Elmer single
channel procedure.
Initial experiments indicated that the presence of magnesium in potassium
solutions causes depression of potassium emission in the Beckman hydrogen-oxy-
gen flame but no such effect in the Perkin Elmer propane-air flame. In addition
the presence of sodium in potassium solutions causes enhancement of potassium
emission in the Perkin Elmer propane-air flame but no such effect in the Beckman

* Duplicate dissolutions were made for all analysis. These were worked out to 4 significant
figures, the duplicates averaged, and rounded off to 3 figures.
 The flame photometric determination of potassium in geological materials 527

Table 1. Biotitc &yak of K (after ccparations) by Perkin Elmer single channel md Bcclunan
proocdurcs,showing Mg depressionof K with the Bcckmon procedure

sample
number P.E. Bcckmon o/oDiffcrcncc

GA 115 4.436 f 0.013 4-43 4.122 f 0.046 4.13 6.7%

4.428 f 0.027 4.137 f 0.022
GA 181 7-117 f 0.020 7-12 6.608 f o-041 6.61 7.1%
7-124 f 0.028 6-613 f 0.022
GA 114 7.254 f 0.018 7.28 6.899 f 0.040 692 4.4%
7-298 & 0.024 6-948 f O-029
GA 113 7-458 f O-025 744 7.197 rt 0946 7.18 3*5%
7.428 f 0.047 7.160 f 0.054
GA 154 6.242 f 0.045 6.22 5.866 f O-099 585 59%
6-203 f 0,027 5-838 f 0.071
GA 180 7-661 f O-034 7-67 7.136 * O-054 7.15 6.8%
7-679 f 0.024 7.171 f O-115
GA 183 6.416 f 0,033 6.40 6-000 i O-037 6.81 6.1%
6.386 & 0.026 6.012 f 0943
GA 186 7.613 f 0.028 7.58 7.129 f 0.043 7-13 5.9%
7.547 f 0.022 7.132 f O-033
GA 187 8.018 f 0.019 7-99 7-782 f 0.036 7.76 29%
7-971 f 0.030 7-734 * 0644
GA 189 6.265 f 0.021 6-27 5959 f o-029 5.93 54%
6-269 f 0.025 5-901 f 0.029
GA 185 6-964 f O-024 6.94 6.716 f O-025 6.6% 3.8%
6.921 f 0.035 6-653 f 0.056
GA 146 6.687 f 0.016 6-66 6.378 f O-024 6.39 4.1%
6-636 f 0.040 6.401 & O-026
GA 145 5-664 i 0.025 5-64 5-305 + 0.028 5.31 58%
5-625 f O-027 5-319 f O-029
GA 156 3.942 f O-037 3-96 3.656 + O-015 3.66 7.5%
3.971 f o-017 3.671 f 0.001
GA 117 7.263 f O-052 7.24 6.817 f O-015 6-82 6.8%
7.224 f O-034 6.832 f O-019
GA 200 7.394 j, 0.025 7.39 7.038 rt 0.014 7.00 52%
7-385 f o-019 7.965 f O-018
GA 195 7.100 f o-035 7-07 6-778 & O-026 6.79 4.0%
7.047 f o-051 6.803 &- 0.026
GA 213 6.803 f 0.016 6.78 6.301 f O-036 6.33 6.6%
6.768 f 0.039 6.355 f O-011

hydrogen-oxygen flame. It was therefore decided to make a full study of the

effects of various cations and anions on potassium emission for the two instruments.

SYSTEMATIC INVESTIBATIONS

A. Overall experimental conditions

The following conditions were Common to all the subsequent investigations.
(i) Flizme ~~t~t~~. A Beckman Model D-U. s~ut~pho~me~r with flame
photometer attachment, Model 9200 and a Perkin Elmer Model 146 flame photom-
eter were used. The Perkin Elmer was employed both aa a single channel, and
as a double channel instrument using lithium as an internal standard.
528 JOHN a. COOPER

The instruments recorded emission of the unresolved potassium doublet at

766.5 and 769.9 m,u. Each instrument was “tuned in” to maximum emission im-
mediately prior to measurements. The Beckman was operated with an oxyhydro-
gen flame fed with oxygen at 14 lb/in2 and hydrogen at 4 lb/in2; the Perkin Elmer
with a propane air flame at 1% lb/in2 propane and 10 lb/in2 air pressure.
Readings were taken, in a continuous run in alternating directions, of multiple
groups (usually seven), with the unknown bracketed between two closely spaced
standards. The root mean square deviation of the transmission readings was
usually about -$ per cent or less.
(ii) Potassium solution. Two concentration levels, containing 3 and 45 p.p.m.
K, were usually selected for study because they were representative of the upper
and lower working ranges encountered. Throughout this work AnalaR K,SO, has
been used as a primary potassium standard. The weight loss on drying at, 120°C.
for 4 hr was co.01 per cent; on heating to 800” for 2 hr the loss was still co.06
per cent. Nevertheless heating to 500°C. has always been carried out, after initial
pulverization. In this laboratory COMPSTONand VERXON, using “Specpure” KC1
as an isotope dilution primary standard, could not obtain reproducible data until
the KC1 had been fused. 41K isotope calibrations against KC1 after fusion matched
41K calibrations against K,SO,. These observations are in accord with thermo-
gravimetric work done by DUVAL (1953). The fused KC1 and the K,SO, were there-
fore regarded as absolute standards. A solut.ion of potassium hydrogen phthalate
(dried for 24 hr at 120°C.) containing 40 p.p.m. K was prepared, with 4 ml 50 per
cent H,SO, per 250 ml. This was run on the Perkin Elmer flame photometer
against a similar 40 p.p.m. K solution made from K,SO,. The rat’io of strengths,
of K H Phthalate solution: K,SO, solution, came to 0.999 + 0,006. This indicated
dried pot’assium hydrogen phthalate is also suitable as a primary potassium
standard.
(iii) Internal standard solution. Li,SO,*H,O AnalaR was heated at 500°C. for
4 hr (DUVAL, 1953), and a solution containing 200 p.p.m. Li was prepared from
the anhydrous salt. This was added, in equal volumes, to the solutions studied.
The resulting 1: 1 dilution must be remembered when studying the graphs.
All cation effects were investigated in the presence of SO,, equivalent to 4 ml 50
per cent H,SO, per 250 ml. This was prepared either as H,SO, for Fe, Al and Ca,
or as (NH,), SO, + (NH,), CO, for Na and Jig. Standard and test solutions were
equivalent in t,his respect in each case.

B. Individual tests and results

(1) Added reagents. Sulphuric acid. Addition of sulphuric acid caused depres-
sion of K emission at both the 3 p.p.m. K and 45 p.p.m. K levels for Beckman
instrument and for the Perkin Elmer used as a single channel instrument (Figs. 1
and 2). Thus at the concentrations used in routine analysis care must be taken to
make the SO, concentrations in the standards and unknowns as close as possible.
Also, not less than 4 ml 50 per cent H,SO, per 250 ml should be used, as shown
by the slope of the depression curve of Fig. 2. Using the Perkin Elmer Internal
St,andard Procedure the readings were unaffected by the H,SO,.
 529
The flame photometric determination of potassium in geological materials

MIS I I H,SO, present

2 4 6 8
a 0
3.0 6
- I
Y
E
%
g 2.8
-\_
75
.u
D
t
r
2.6
t

Fig. 1. Effect of added H,SO, (in 250 ml) on K emission of K,SO, solution at
3 p.p.m. K level.
x Beckman
0 P.E. Single Channel
l P.E. Internal Standard
‘f Atomic Absorption

MIS. 1.1 H&O, present

Fig. 2. Effect of added H,SO, (in 250 ml) on K emission of K,SO, solution at
45 p.p.m. K level.
x Beckman
0 P.E. Single Channel
0 P.E. Internal Standard
530 JOHN A. COOPEH

Ammonia (as sulphate) and ammonium carbonate

Potassium solutions of two strengths, 40 p.p.m. K and 4 p.p.m. K respectively,
were prepared containing
(a) 4 ml 50 per cent H,SO,,
(b) 4 ml 50 per cent H&O, neutralized with ammonia,
(c) 4 ml 50 per cent H,SO, neutralized with ammonia + 5 ml 10 per cent
(NH,), CO,.
The three solutions of each level were measured against each other in sequence,
the results averaged and set out in Table 2.
Table 2. Comparison by three measuring procedures of K emission from
solutions at 40 and 4 p.p.m. levels containing (a) 4 mls of 50 per cent H&l04 in
250 ml. (b) (a) neutralized with ammonia (c) (b) with 5 ml 10 per cent
(NH&&O, included

40 p.p.m. K level

P.E. P.E.
single Int.
Beckman channel Std.

(4 &SO4 100.0 998 99.8

(b) (NH&SO, 94.6 100.0 99.9
(c) (NH&SC, + (NH,)&% 94.6 99.7 100.0

4 p.p.m. K level

P.E. P.E.
single Int.
Beckman channel Std.

(4 &SO4 100-O 100.0 100.0

(b) (NH&SC, 93.4 99.4 99.0
(c) (NH&SO, + (NH,)&% 89.0 93.0 93-7

At the 40 p.p.m. K level the Beckman procedure shows depression by both re-
agents. Neither of the Perkin Elmer procedures are affected. At the 4 p.p.m. K
level all procedures show depression by both reagents. This confirms the need for
keeping such added reagents at the same level in both standard and unknown
solutions.

Perchloric acid
Perchloric acid (Fig. 3) gave similar results to those observed for sulphuric acid
but, in addition, caused some depression of K-emission using the internal standard
procedure with the Perkin Elmer.
(2) Elements not removed with the R,03 group and Calcium.

Sodium
A 1000 p.p.m. sodium solution was prepared from AnalaR Na,SO,. Dilutions
of this were incorporated in the test solutions.
 The flame photometric det,ermination of potassium in geological materials 531

Ms. HCLO Present

24 I

Fig. 3. Effect of added HClO, (in 250 ml) on K emission of K,SO, solution at
3 p.p.m. K level.
X Beckman
0 P.E. Single Channel
0 P.E. Internal Standard

3.6

Y 3.4 -

t
20 40 60 80 100 120 140 I60 180

PPM. No present

+ 0.3 grms plagioclose L

C 03 grms hornblende __C
t 0.3 grms shale t
f 03 grms basalt __)
IO grms oeger,ne - - - - - - - - - - - - - - -
ft IO grms pyro*ene

Fig. 4. Effect of added Na on K emission of K,SO, solution at 3 p.p.m. K level

with (NH&SO, + (NH&COB present in standard and test solutions.
x Beckman
o P.E. Single Channel
l P.E. Internal Standard
‘J’ Atomic Absorption

3 p.p.m. K (Fig. 4)
The Beckman showed no measurable variation in potassium emission with
increasing Na content. The Perkin Elmer single channel procedure showed en-
hancement, up to 15 per cent for the sodium contents simulating albite. The
greatest relative effect is seen at low concentrations of Na. The Perkin Elmer
Internal Standard Procedure was similarly affected, but to a lesser degree than
the single channel procedure.
532 JOHN A. COOPER

45 23.p.m. K (Fig. 5)
No significant effect by Na on K is shown in the ranges to be encountered.
(However, see trachyte analysis in Table 4.)
These results follow the trend of Poluektov’s graph (Fig. 6) for air acetylene
work, but to a smaller degree because propane-air was used here.

46

Y
P
z 45
D
L
x
n
c PPM. No present

+ O-I qrms Kfeldspar -

-+-0.15 grms shale -

Fig. 5. Effect of added Na on K emission of K,SO, solution at 45 p.p.m. K level

with (NH&SO4 + (NH&CO, present in standard and test solutions.
x Beckman
0 P.E. Single Channel
l P.E. Internal Standard

I 00 % c 57/MI K

Acetylene -w flame. (after Poluektov)

tOOy/Ml K

Mgrms /ml Na present

Fig. 6. Effect of added Na on K emission at 5, 10, 40 and 100 p.p.m. K levels

using an air acetylene flame (after POLUEKTOV,1961).
 The flame photometric determination of potassium in geological materials 533

Magnesium
1000 p.p.m. Mg solution was prepared from MgSO,.7H,O and dilutions of
this incorporated in the test samples.

3 p.p.m. K (Fig. 7)
Here is shown a gross depression of unusual characteristic with the Beckman
procedure, and small enhancements of unusual characteristic using the Perkin
Elmer procedures.

Y
WM. Mg present

100 300 1000

y 2.9 It I
s
si
a
0
a
\
H 2’8
8
0
C
25
I
\

2.6

a 03 grms hornblende __c

* 0.3 guns shale -c

- 03 grms basalt

4 IO grmspyroiene
Fig. 7. Effect of added Mg on K emission of K,SO, solution at 3 p.p.m. K level
with (NH&SO, + (NH&CO, present in standard and test solutions.
x Beckman
0 P.E. Single Channel
0 P.E. Internal Standard
y Atomic Absorption

45 p.p.m. K (Fig. 8)
Using the Beckman instrument the intensity of the potassium emission was
strongly depressed. No effect was observed using the Perkin Elmer either with
the single channel or internal standard procedures. This indicates that the Perkin
Elmer K values for biotites in table 1 are correct and that the Beckman figures
are low. Identical curves were obtained with H,SO, present instead of neutral
sulphates.
(3) Elements removed with R,O,, and Calcium. The effects of Ca, Fe and Al
were investigated at the 3 p.p.m. K levels only, since the other interferences
studied seem greater at these lower potassium levels. Measurements were made
in a sulphuric acid medium throughout, simulating mineral dissolution.
534 JOHN A. COOPER

PPM Mg present
20 30 40 50 60 70 60

@I6 grms. blotite C

e O-3 grms. shale -

Fig. 8. Effect of added Mg on K emission of K,SO, solution at 45 p.p.m. K level

with (NH&SO, + (NH&CO, present in standard and test solutions.
x Beckman
0 P.E. Single Channel
l P.E. Internal Standard

PPM Co present
20 40 60 80 y IOO 120 '40 '60
30 t 1 t * I I 0 I ^
i 8 0 e
Y 0
I X X s
k
a 2.8- -X --

Y
0 I
0 3 grms hornblende c

2.6 pp 0 3 grms plagloclase c

e 0.3 grms sha;e -›,

4- 03 grms basalt --t

s‘ I.0 wnr. pyroxcne

Fig. 9. Effect of added Ca on K emission of K,SO, solution at 3 p.p.m. K level

with H,SO, present in standard and test solutions.
x Beckman
0 P.E. Single Channel
l P.E. Internal Standard
y Atomic Absorption
 The flame photometric determination of potassium in geological materials 535

Calcium solution was prepared as nitrate from CaCO, and HNOs excess HN03
being removed by heating. The amount of SO, in standards and unknowns would
buffer out any effect of the small residual nitrate. Fig. 9 shows that the Beckman
procedure reoords depression of K emission whilst the Perkin EImer procedures
were both unaffected.

Al~~~n~~~ (3 +p.p.rn.K, Fig. 10)

Aluminium sulphate was prepared from Al metal and H,SO, + HCI, excess
acids being fumed off.
Fig. 10 shows that the Beckman and Perkin Elmer single ohannel procedures
both suffer depression of K emission. The Perkin Elmer internal standard
procedure is unaffected.

l?f?M. Al present
50 loo 150 200
Y 250
3.0

= 2.6 -
i
E
t
B
_;
8 - CT3 grms. hornblende
5 2.6
-t
- 03 grms ploglcdase

03 grms shale

t-
I.0 grms.
L-“““-
pyroxene
03 grms

Fig. 10. Effect of added Al on K emission of K&40, solution at 3 p.p.m. K level,

with H2S0, present in standard and test solutions.
bosoii

x Beckman
0 P.E. Single Channel
l P.E. Internal Standard
y Atomic Absorption

Iron (3 p.p.na. K, Fig. 11)

Iron solution was prepared from Fe metal, H2SOr and. HCl. Exoess aoid
was fumed off, the residue dissolved in water, and about 10 per cent oxidized by
boiling after addition of a little concentrated HNO,. Fig. 11 shows that the
Beckman prooedure suffers gross enhancement of K emission.
The single channel Perkin Elmer procedure shows enhancement only at high
Fe levels. It is interesting to note that the Perkin Elmer internal standard is in
this ceaseaffected more than the single channel procedure.
(4) Atomic absorption meamrernents. Through the courtesy of D. J. DAWN
(C.S.I.R.O., Canberra), a number of atomic absorption readings were made using
an acetylene-air flame. These have been plotted on the respective graphs and
536 JOHN A. COOPER

X/
d
,
-x &A-j 100 35.0 1000
0 30
WM. Fe present

- 03 grms hornblende-

03 grms shale

- O-3 grms basalt

- I.0 grms pyroxene

Fig. 11. Effect of added Fe on K emission of K,SO, solution at 3 p.p.m. K level

with H,SO, present in standard and test solutions.
x Beckman
0 P.E. Single Channel
l P.E. Internal Standard
)’ Atomic Absorption

serve to illustrate that this procedure can also suffer similar real interferences in K
determinations.
DISCUSSION
These results in general suggest that the deviations observed are controlled by
the type of burner used, the composition of the fuel gases and the resultant flame
temperature. BAKER and GARTON (1961) report similar conclusions. The Unicam
BP900 and the E.E.L. instruments, which use a Mekker Type burner and pro-
pane-air as fuel, would thus be expected to behave similarly to the Perkin Elmer
as a single channel instrument. If a total consumption type burner using hydrogen
and oxygen is employed, the results should be affect’ed as shown here with the
Beckman, whereas with a total consumption type burner using acetylene-air, devi-
ations reported by POLVEKTOV (1961) would occur. Using acetylene oxygen the
effects reported by ABBEI’ and MAXWELL (1960) and HAVRE (1961) would be
present.
The three procedures, with and without separation of R,O, and Ca, are tabu-
lated with interferences in Table 3.
The result of a number of interferences acting together is uncertain although
 Table 3. Interferences to flame photometric K determination, due to the presence of other elements
inferred from experimental datd on synthetic solutions
- indicates depression, + indicates enhancement, ( ) indicates inferred from low level work and probably very small.

P.E. Single Channel P.E. Internal Standard

Other
Beckman Procedure Procedure Procedure
Approx :. major
Mineral
% K elements
B0f0r0 After Before After Before After
present
Separations Separations Separations Separations Separations Separations

Biotites 7 Al, Fe, Mg Mg- (Al-) Mg- <Al-) Nif Nil Nil
(Fe+)
Muscovites 8 Al (Al-) Nil (Al-) Nil Nil Nil
Plagioclases 0.2-1.5 Al, Ca, Na Al, Ctt Nil Al-, Na+ N&+ N&+ Nat
Hornblendes o-2 Al, Fe, Ca, Al-, Fe+, Ca-, Mg- Al-. Na+ Na+ N&“, Na+,
Mg, Na Mg- (possibly Mg+) (possibly Mg+)
K-feldspars 9-14 Al, Na (Al-) Nil Al- Nil Nil Nil
Pyroxenes 0.1 Al, Fe, Ca, Al-, Fe+, Cla-, Mg- All (possibly Fe+) (possibly Mg+) Fe+ (possibly Mg*)
Mg, (I-t Na) Xg- (possibly Mg+) (possibly Mg+)
Basalts 0.2-1,3 Al, Fe, Ca, Al-, Fe+, Ca-, Mg- A-, Na+, Fe+ NC%+ Net Nat
Mg, Na Mg-
Shales 2-6 Al, Fe, Ca, Al-, Fe+, Ca-, Mg- Al--, Na+ Na’ Na+
Mg, Na Mg-
538 JOEN A. COOPER

it is to be expected that some would counteract each other. The “Beckman Pro-
cedure without chemical separations” could be satisfactory only for K-feldspars
and muscovites. The “Beckman Procedure with separations” is useful for all feld-
spars and normal muscovites. K emission is depressed by Al in the “Perkin Elmer
Single Channel Procedure without chemical separations” (when K is low), whereas
sodium causes considerable K enhancement except in the higher potassium miner-
als, i.e., micas and K-feldspars. The “Perkin Elmer Single Channel Procedure”
(with chemical separations) is affected by Na enhancement only, and then not
detectably if K is high.
The “Perkin Elmer Internal Standard Procedures” suffer least from inter-
ferences. They are not sensitive to variations in SO, content, which is a distinct
advantage as “fuming off” procedures are involved in the chemical treatment of
samples. However, sodium enhancement remains at low K levels, although to a
lesser degree than in the “single channel procedures”. Also Mg seems to cause
slight enhancements (up to 1 per cent) at low K levels. Very high Fe content, as
in some pyroxenes, would cause K enhancement, although separations can remove
this.
The ultimate aim of an investigation such as this is the development of a pro-
cedure for K analysis that may be applied to samples of all compositions and
requires the minimum of manipulation. Although it might seem at first that the
answer is to separate all interfering ions, customary separation procedures will
leave both Na and Mg in solution. It has been shown that both of these can be
strongly interfering. Further, it is now known that the ammonia-ammonium
carbonate precipitation, as adopted from SCOTT (1953) allows most of the Ca to
remain in solution (MARTIN, 1962, personal communication). This results in
slightly low K values for some feldspars when using the Beckman instrument. In
addition, it can be deduced from the Na effects shown in Fig. 4 that a sodium
buffer technique (i.e., the addition of a large excess of Na to both standard and
unknown solutions in equal amounts) is required for both Perkin Elmer proce-
dures, even when separations have been carried out. The result of such buffering,
when K content is low, is illustrated for the Perkin Elmer Single Channel Procedure
in Table 4.
The Perkin Elmer Internal Standard Procedure without chemical separations
and with the addition of a Na buffer very nearly satisfies the requirements. Figs.
6 and 10 indicate that very low potassium levels could suffer slight magnesium
enhancement and that excessive Fe should be avoided (e.g., some pyroxenes).
Subsequent tests have shown that the Na buffer almost eliminated the Mg en-
hancement but not that due to very high Fe content. However this Fe enhance-
ment has been looked for, but not detected, in several critical samples when using
this procedure.
The use of “no separation, Li internal standard, Na buffer” (see Appendix II)
has now been adopt’ed for all silicates except highly differentiated pegmatite
materials. These materials present a separate problem due to the presence of
lithium, which alters the internal standard content, as well as rubidium and cesium
which have been reported to give rise to interalkali emission effects (FAXJUHAR
and HILL, 1962). The chemistry routine set out in Appendix II should control
 The flame photometric determiuation of potclssium in geological materials 639

Table 4. The enhancement of potassium emission by sodium at low H levels, is reduced by

buffering unknown and standard solutions with 600 p.p.m. Ne (P.E. single channel, with
chemical separation).
Approx. Approx. o/oenhance-
p.p.m. K p.p.m. Na ment of
Sample in dn. in sol’n. o/oK before buffering o/0 K after buffering KbyNe

Eclogita (9) RVII 2.7 22 0.225 & 0.001 0.225 O-208 f O-002 0.207 7.2
0.225 k 00l1 0.205 f 0.001
Basalt H2 3.5 14 0.288 k 0.001 0.287 0.268 rt O-001 0.268 7.1
0.285 & O@Ol 0.268 f 0.002
Eclogite ( 4) 3.9 8 0.318 & 0.002 0.318 0.307 f 0.002 0,307 3.6
RVIII 0.318 k 0.001 0.307 f 0.002
Bdt H5 4-o 21 0.320 f 0.002 0.320 0.293 * 0.001 0.292 9.6
0.319 &- O+Ol 0.291 f 0.001
Basalt H6 4.3 21 0.349 & 0.001 0.348 0.315 f 0.002 0.315 10.5
0.347 f 0.002 0.314 f 0.002
Badt H3 4.5 21 0,380 & 0.001 0.380 0.361 f o-004 0.351 8.3
O-381 f 0.002 0.351 + 0.002
Bdt Hl 6.0 16 0.479 f 0.003 0,477 0.446 & 0.004 0.445 7,2
0.475 f 0.004 0.444 f 0+)03
Trechyte H33 9 28 l-118 k 0.002 1.10 l-069 f 0.006 1.06 3.8
1.093 f O-006 l-061 & 0.007
Eclogita (1) RVIV 21 9 1.779 f 0.004 1.78 1.754 & 0.014 1.76 1.1
1.778 -& 0.003 1.765 & 0.020
Trachyte H32 21 46 2.079 f 0.005 2.09 2.037 + 0.012 2.03 3.0
2.101 * 0.009 2.025 k 0.019
TrsGhyte H60 28 42 4.342 f 0.022 4.36 4.250 + 0.017 4.24 2.8
4.370 f 0.026 4-223 + 0.036
Trechyte H43 27 58 2.917 f 0.013 2.91 2.821 f 0.014 2-82 3.2
2.908 i O-018 2.813 + 0.017
Trmhyte H7 38 50 3.981 f 0.020 3.99 3.983 + 0.020 3.99 0.0
3.990 I 0.018 3.995 * 0.002

these effects using the Perkin Elmer flame photometer as a single channel and not
as an internal standard instrument. However the potassium readings would be
enhanced by direct emission from the Rb 7800 A line which is not fully resolved
by the optics of this instrument.
I. D. MARTIN of this department has made a separate study of these elements
and his results will be published soon.

VALIDITY OF RESULTS
Comparieon 0J’jiame photometric and isotope dilution potassium analysis
COMPSTON and VERNON have analysed a number of samples for potassium by
isotope dilution. Their results are compared with flame photometric figures in
Table 5. The agreement at the lower levels is very satisfactory particularly with
the plagioclases. This comparison shows a spread of several per cent between the
two methods for some samples but reasonable agreement with others. HART (1961)
reported a similar comparison with the same overall result. However in this work
the precision of the flame photometry is much better than 1 per cent.
Also in Table 5 are shown the flame photometric potassium determinations of
a number of National Bureau of Standards and other interlaboratory samples.
These are compared with recommended values. Some are very close whereas
others indicate that accepted values may need reviewing.
 0”
Table 5. Comparison of flame photometric potassium determinations on minerals with (a) Isotope dilution analysis (Compston and
Vernon), (b) Recommended values of ~~rl&bor&tory standards (a indicates single analysis).

% H % H % H
P.E., P.E., % K Isotope
Direct Reading Direct Reading P.E., Dilution % B
Chem. Separ- Chem. Separ- Li Int. Std. (Compston Previously
ations No ations + Na No Separations and Recommended
Sample No. Stunple buffer btier i_ Na buf3Fes Vernon)

GA 394 Plagioolase 0*250 8.

“o:;;j 0.251

GA 395 Plagioolase 0.497 8.

;:;t;;) 0.498

GA 396 Plagioclase 0.256 s.

GA 393 Pf&$iocl&se 0.6786

0.6685 (9) 0,693 s.

GA 508 Pyxoxene 0.203

GA 510 Pyroxene o*o43Q 0.045

0.043
a.0450 I

GA 466 Whole Rock O-387

R441A-1 Mus~ovi~ 8.77

GA 509 Hornblende 0,227 8.

GA 49 Biotite 769
The flame photometric determination of potassium in geological materials 541
Table 6. Comparison of K-Ar ages obtained using different minerals from the one rock, indicating consistency in analysis with varying
matrix and extremes of K concentration

% K
(Duplicate K-Ar age
Rock Type Sample K Determination Procedure dissolutions) ( x 108)

Whole Rock P.E. Single Channel, Chem. 0.2894 0.2853 165

Separations, Na buffer

Dolerite (a) P.E. Single Channel, Chem. 0.1893

Separations, Na buffer Argon
Plagioclase (b) P.E. Li Int. Std., No 0.1894 161 determinations
Separations, Na buffer and Age
2
calculations
Whole Rock P.E. Single Channel, Chem. 0.5604 05613 1051 1
by
Separations, Na buffer I. McDougall ?
Dolerite Pyroxene P.E. Li Int. Std., No 0.1859 0.1847 1029
Separations, Na buffer

Biotite P.E. Li Int. Std. no separ- 6.012 6.025 172, 173

Pegmatitic ations, Na buffer Duplicate
Pyroxene P.E. Li Int. Std., no separ- 0.2134 0.2138 171, 173 Argon
Dolerite ations, Na buffer runs
Plagioclase P.E. Li Int. Std., no separ- 0.6132 0.6133 170,166
ations, Na buffer

Plagioclase* P.E. Single Channel, Chem. 0.6781 0.6764 158

Dolerite Separations, Na buffer
Pyroxene P.E. Li Int. Std., no separ- 0.1103 0.1121 153
ations, Na buffer

Biotite P.E. Li Int. Std., no separ- 6.927 6.947 371

Adamellite ations, Na buffer
Hornblende P.E. Li Int. Std., no separ- 0,4639 0.4616 376
ations Na buffer
 Biotite P.E. Li .Int. Std., no separ- 7653 7643 370
Xenolith ations, Na buffer
from Hornblende P.E. Li Int. Std., no separ- 05113 05156 375
above ations, Na buffer

Biotite P.E. Li Int. f,td., no separ- 7.518 7.516 244

Adamellite ations, Na buffer
Hornblende P.E. Li Int. Std., no separ- 0.7506 0.7475 246 Argon
ations, Na buffer determinations
and Age
Biotite P.E. Li Int. Std., no separ- 7.058 7.060 34 calculations
Analcite ations, Na buffer by
Basalt Kaersutite P.E. Li Int. Std., no separ- 1.399 I-391 34 J. It. Richards
ations, Na buffer

Pyroxene P.E. Li Int. Std., no separ- 0.0903 O*OSQl 171

Dole&e ations, Na buffer 0.0928
Plagioclase P.E. Li Int. Std., no separ- 0.2146 0.2166 168 Duplicate
ations, Na buffer 170I Argon runs

Biotite P.E. Single Channel, Cbem. 6.765 6.736 225

Adamellite Separations
Hornblende P.E. Li Int. Std., no sopar- 1.512 l-520 221
ations, Ne buffer

Biotito P.E. Single Channel, Cbem. 6.367 6.327 1360

Pegmatitic Separations
aranite Muscovite P.E. Li Int. Std., no separ- 9.144 9.132 1351
ations, Na buffer
544 JOEN A. COOPER

Comparison of K-Ar ages of different min,erals from the one rock

A number of K-Ar ages have been determined for different minerals extracted
from the one rock. These minerals have very different K contents, a factor of up
to 1: 60 being involved. Some of these are listed in Table 6. The generally good
agreement shown between these results is usually regarded as an,indication of
argon retention by the minerals involved. However it is also an indication of
correct potassium analysis as errors here would also cause disagreement in the
ages obtained.

Acknowledgements-The K-Ar dates were made available by Drs. J. R. RICHARDS and I,

MCDOUGALL.
Dr. W. COMPSTONand M. J. VERNON carried out the isotope dilution analyses.
To these people acknowledgement is gratefully recorded.

REFERENCES

ABBEY S. and MAXWELL J. A. (1960) Determinat,ion of potassium in micas. ClLem. Canad. 12, 9.
37-41.
AHRESS L. H. and FLEISCHEB M. (1960) Investigation of the composition of two silicate rocks.
U.S. Geol. SW-V. Bull. 1113, 83-111.
BAKER C. A. and GARTON F. W. J. (1961) A study of interferences in emission and absorption
flame photometry. Report AERE-R-3491, Atomic Energy Research Establishment, England.
ConmsToN \V. and VERNON &I. J. (1962) Personal communication.
DEAN J. A. (1960) Flame Photometry; McGraw-Hill, New York.
DECAL C. (1953) Inorganic Thermograwimetric Analysis; pp. 145-146. Elselvier, New York.
EVERNDEN J. F. and RICHARDS J. R. (1962) Potassium argon ages in Eastern Australia. J. Geol.
Sot. Aust. 9,1, l-50.
FARQUHAR M. C. and HILL J. A. (1962) Analysis of cesium and rubidium salts and metals.
Anal@. Chem. 34, 222-224.
HAMILTON E. (1962) Storage of standard solutions in polythene bottles. Sature, Lund. 193,
4811, p. 200.
HART S. It. (1961) The use of hornblendes and pyroxenes for K-Ar dating. J. Cr’eophys.Res. 166,
9, 2295-3001.
HAVRE G. N. (1961) The flame photometric determination of sodium, potassium and calcium in
plant oxtracts wit’h special reference to interference effects. Analyt. Chim. Acta, 25, 557-566.
KULP .J. L. (1961) Geologic time scale. Science 133, 3459, 1105-1114.
MARTIN I. D. (1962) Personal communication.
?;ATIONAT~BUREAU OF STANDARDS (1959) Circular 552 (3rd Edition).
PISSOT \V. H. (1958) Variations in isotopic abundances of strontium, calcium and argon and
rolat’cd t,opics. 11. I. T. Sixth Annual Progress Report, for 1958, NYO-3939, 5-27.
PINSOS \V. H. (1961) BI.1.T. Ninth Annual Progress Report for 1961, NYO-3942, p. 276.
POLIJEI~TOV N. S. (1961) Techniques in flame Photometric Analysis (Russian Translation).
SolJle Offset Printers.
SCOTT \I’. \V. (1939) Scott’s Standard Methods of Chemical Analysis, 1,p. 866. Van Sostrand,
New York.
VERNON 31. .J. (1962) Personal communication.

APPENDIX 1

Potassiuwb determination as used by E,uernden and Richards (1962)

About 0.8 g of the mineral was extracted from the whole of the original sample by successive
halving with a microsplitter. This was placed in a cleaned “Wig-L-Bug” dental amalgamator
ball mill, with two balls, and ground.
 The flame photometric dct,ermination of potassium in geological materials 545

Grinding times: micas-10 min

others-3 min

Seven samples were run in duplicate as below.

Approx. sample weight taken: biotites-0.16 g

muscovites-0.16 g

plagioclases-
0.30 g
hornblendes -1

K-feldspars-0.12 g

Weigh powdered samples into a 70 ml platinum dish.

Add exactly 4 ml 50 per cent H,SO, (Analar) + 25 ml HF (Merck or Bakers).
Place on a water bath and evaporate slowly down. Add 10 ml HF and evaporate down again.
Add 2 ml cone. HNO,, swirl and leave on the water bath for another 5 min.
Transfer dishes to a hot plate and heat to the first sign of H,SO, fumes.
Cool, add 50 ml H,O, return to the water bat,h and evaporate down.
Add 50 ml H,O, warm to solution and transfer t,o a 250 ml tall Pyrex beaker using a fine jet
wash bottle (Stage A).
Bring to the boil on a hot plate. Cool.
Add 10 ml volume of pre-washed Whatman cellulose powder, 5 drops of bromocresol green
indicator solution, and neutralize to a blue colour with ammonia whilst stirring.
Add 5 ml 10 per cent ammonium carbonate (Analar) solution.
Warm on a hot plate, cool and allow to stand for one hour.
Filter through a washed Whatman 540 filter paper (12.5 cm) into a 250 ml volumetric flask.
Wash precipitate 12 times with water.
Dilute to volume, mix and store in a 250 ml polythene bottle.
Standard K solutions were prepared at convenient concentration intervals (e.g., 40 and 50, 8
and 10 p.p.m. K) in 2-1. quantities, from analar K,SO, previously ignited to 500°C. They incor-
porated exactly the same quantities of neutralised H&O, and (NH&CO, as is used above. All
dilutions were gravimetric except the last which was made t,o volume. Fresh weighings of K,SO,
and subsequent dilutions were made for each preparation of standards.
The flame photometer was first adjusted by moving the wavelength selector to give maximum
reading on the desired peaks, and then set to give almost full scale deflection for the higher of the
two standards, which were chosen to bracket t,he unknown solution. After zero adjustment,
seven runs were made in alternate directions without any further alteration of controls. The
result of the seven runs were averaged. The standard error of each measurement series was
+& per cent,, although agreement between duplicat,e dissolutions was quite often better.
Micas and hornblendes were determined using t,he Perkin Elmer 146 instrument,. Feldspars
were determined using the Beckman D.U. instrument. (However set discussion above.)
For satisfact)ory work on neutral salt solutions the following maint,enance was essential.
(1) Perkin Elmer.
After each sample run the flame was extinguished, the at,omised jet extracted and rinsed to
remove salt encrustations. The burner was removed and cleaned daily.
(2) Beckman.
The jet n-as removed daily and an aqueous detergent mixt,ure was suckrd back through the
hydrogen ant1 oxygrn j&s. Tlley were then rinsed similarI>- xit,h distillccl water.

Storaye oj solutio~9
Solutions ~vere generally stored in polythene bot,tles. Howovcr, recent diffusion experiments
by H.MILTON (1961) and \7~~~~~ (personal communication, 1962) show that such containers
suffer significant liquid loss n,ith time. For this reason standard solutions were rejected and
remade every :%-4months. I)il\ltion trlats showed that tllis time may be ql~adruplcd if an internal
standart is used.
546 JOHN A. COOPER

APPENDIX II
Recolnmended procedure for potassium determination-s
Except that 6 ml of 50 per cent H&O, are now used, the treatment is the s&me8s in Appendix
I up to Stage A, of transferring to end boiling in a 250 ml beaker.
(Note: A few samples, p8rticularly pyroxenes, where larger semple weights 8re taken, 8nd
occctsionally hornblende8 and pkbgioclases, resist complete dissolution. They thus give slightly
low analyses with comperatively poor duplication. To these, 15 ml of low K HCl is added before
the second addition of HF when on the water bath. This HCl must be gently fumed off before
edding the HNO, to prevent etching of the pletinum. Alternatively 10 ml of perchloric 8cid is
8180added 8t the beginning. In this c8se no HNO, is used, the whole is fumed to dryness under
an infra-red 18mp, and another 6 ml of 50 per cent H,SO, is subsequently added.)
To this solution, at St8ge A, 100 ml of 8 1250 p.p.m. Na + 500 p.p.m. Li solution are added
from a well siliconed and rec8librated pipette. The solution is traneferred to 8 250 ml volumetric
fl8sk 8nd mede to volume. The added alkali strengths ere now 600 p.p.m. Na and 200 p.p.m. Li.
These solutions 8re compared with standard potassium solutions containing equivalent
8mounts of H,SO,, Ns and Li, by bracketing, 8s in Appendix I, but using the Perkin Elmer
intern81 standrtrd procedure.
The lithium solution is prepared from B.D.H. LiCl, which, although extremely hygroscopic,
contains very little potassium. Two 1. of approximately 20,300 p.p.m. Li solution 8re prepared.
This is stored in 8 pyrex bottle that he8 been fitted with 8 standard B34 ground glass neck. A
Teflon sleeve is placed on the stopper which is pressed home herd. Evaporative losses should
thus be reduced to 8 minimum. The bottle itself is cleaned with 8 dilute HF detergent mixture,
rinsed, dried, coated with silicone, rinsed with acetone and dried. (For very low K levels 8
Specpure Grade of Li salt is used.)
20*000g of 20,000 p.p.m. Li solution end 3.0892 g of anhydrous Ne,SO, (An&r) are ticor-
porated in each 2 1. of standard potassium solution.
The 1260 p.p.m. Ne + 500 p.p.m. Li solution, for adding to unknowns, is made by taking
60*000 g of 20,000 p.p.m. Li solution + 7.7230 g anhydrous N+SO, to 2 1. This is stored in 8
gl8as bottle sin-&r to the 20,000 p.p.m. Li solution.
The comperieon standards, containing both K and Li in required strengths end ratios, are
stored in 2-1.hard polythene bottle8 that have hard, tight locking csps.